Organic electroluminescent materials and devices

Abstract

Ligands with fused spirocyclic substitutions and metal complexes formed with such ligands and having improved performance in OLED applications are disclosed.

We claim: 
     
       1. A compound comprising a first ligand L A  having a structure according to Formula 1: 
       
         
           
           
               
               
           
         
         wherein rings A and B are each a 5 or 6-membered carbocyclic or heterocyclic ring; 
         wherein R A  and R B  each independently represent a mono substitution or up to the maximum possible number of substitutions, or no substitution; 
         wherein Z 1  and Z 2  are each independently selected from the group consisting of carbon or nitrogen; 
         wherein Z 1  is a neutral donor atom; 
         wherein each R A  and R B  is independently a hydrogen or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; 
         wherein any adjacent substituents are optionally joined or fused into a ring; 
         wherein at least one pair of R B  are joined or fused into an aromatic ring; 
         wherein at least one R A  comprises (1) a spiro polycyclic alkyl fused to an aromatic ring; or (2) a spiro polycyclic alkyl fused to ring A; 
         wherein the ligand L A  is coordinated to a metal M; 
         wherein the metal M can be coordinated to other ligands; and 
         wherein the ligand L A  is optionally linked with other ligands to comprise a tridentate, tetradentate, pentadentate or hexadentate ligand. 
       
     
     
       2. The compound of  claim 1 , wherein M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Au, and Cu. 
     
     
       3. The compound of  claim 1 , wherein M is Ir or Pt. 
     
     
       4. The compound of  claim 1 , wherein Z 1  is a neutral nitrogen donor atom or a neutral carbene donor atom. 
     
     
       5. The compound of  claim 1 , wherein ring B is benzene. 
     
     
       6. The compound of  claim 1 , wherein ligand L A  is selected from the group consisting of: 
       
         
           
           
               
               
           
         
       
       wherein X is selected from the group consisting of O, S, Se, C, Si and N. 
     
     
       7. The compound of  claim 1 , wherein the spiro polycyclic alkyl group is selected from the group consisting of: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
       8. The compound of  claim 1 , wherein ligand L A  is selected from the group consisting of: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
       9. The compound of  claim 1 , wherein the compound has a formula of M(L A ) n (L B ) m-n ;
 wherein M is Ir or Pt; L B  is a bidentate ligand; 
 wherein when M is Ir, m is 3, and n is 1, 2, or 3; and 
 wherein when M is Pt, m is 2, and n is 1, or 2. 
 
     
     
       10. The compound of  claim 9 , wherein the compound has a formula of Ir(L A ) 3 , Ir(L A )(L B ) 2  or Ir(L A ) 2 (L B ), wherein L B  is different from L A ; or the compound has a formula of Pt(L A )(L B ), wherein L A  and L B  can be same or different. 
     
     
       11. The compound of  claim 9 , wherein L B  is selected from the group consisting of: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein each X 1  to X 13  are independently selected from the group consisting of carbon and nitrogen; 
         wherein X is selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO 2 , CR′R″, SiR′R″, and GeR′R″; 
         wherein R′ and R″ are optionally fused or joined to form a ring; 
         wherein each R a , R b , R c , and R d  may represent from a mono substitution up to the maximum possible number of substitutions, or no substitution; 
         wherein R′, R″, R a , R b , R c , and R d  are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and 
         wherein any two adjacent substituents of R a , R b , R c , and R d  are optionally fused or joined to form a ring or form a multidentate ligand. 
       
     
     
       12. The compound of  claim 8 , wherein the compound is Compound Ax having the formula Ir(L Ai )(L Bj ) 2 , wherein x=300i+j−300; i is an integer from 120 to 131, and j is an integer from 1 to 300; or
 the compound is Compound By having the formula Ir(L Ai ) 2 (L Bj ), wherein y=300i+j−300; i is an integer from 120 to 131, and j is an integer from 1 to 300; or 
 the compound is Compound Cz having the formula Ir(L Ai ) 3 , wherein z=i; i is an integer from 1 to 131; and wherein L B  is selected from the group consisting of: 
 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
       13. An organic light emitting device (OLED) comprising:
 an anode; 
 a cathode; and 
 an organic layer, disposed between the anode and the cathode, comprising a compound comprising a first ligand L A  having a structure according to Formula 1: 
 
       
         
           
           
               
               
           
         
         wherein rings A and B are each a 5 or 6-membered carbocyclic or heterocyclic ring; 
         wherein R A  and R B  each independently represent a mono substitution up to the maximum possible number of substitutions, or no substitution; 
         wherein Z 1  and Z 2  are each independently selected from the group consisting of carbon or nitrogen; 
         wherein Z 1  is a neutral donor atom; 
         wherein each R A  and R B  is independently a hydrogen or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; 
         wherein any adjacent substituents are optionally joined or fused into a ring; 
         wherein at least one pair of R B  are joined or fused into an aromatic ring; 
         wherein at least one R A  comprises (1) a spiro polycyclic alkyl fused to an aromatic ring, wherein the aromatic ring is directly bonded to ring A; or (2) a spiro polycyclic alkyl fused to ring A; 
         wherein the ligand L A  is coordinated to a metal M; 
         wherein the metal M can be coordinated to other ligands; and 
         wherein the ligand L A  is optionally linked with other ligands to comprise a tridentate, tetradentate, pentadentate or hexadentate ligand. 
       
     
     
       14. The OLED of  claim 13 , wherein the organic layer is an emissive layer and the compound is an emissive dopant or a non-emissive dopant. 
     
     
       15. The OLED of  claim 13 , wherein the organic layer further comprises a host, wherein the host comprises a triphenylene containing benzo-fused thiophene or benzo-fused furan;
 wherein any substituent in the host is an unfused substituent independently selected from the group consisting of C n H 2n+1 , OC n H 2n+1 , OAr 1 , N(C n H 2n+1 ) 2 , N(Ar 1 )(Ar 2 ), CH═CH—C n H 2n+1 , C≡CC n H 2n+1 , Ar 1 , Ar 1 -Ar 2 , and C n H 2n —Ar 1 , or the host has no substitutions; 
 wherein n is from 1 to 10; and 
 wherein Ar 1  and Ar 2  are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof. 
 
     
     
       16. The OLED of  claim 13 , wherein the organic layer further comprises a host, wherein host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene. 
     
     
       17. The OLED of  claim 13 , wherein the organic layer further comprises a host, wherein the host is selected from the group consisting of: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       and combinations thereof. 
     
     
       18. A consumer product comprising an organic light emitting device comprising:
 an anode; 
 a cathode; and 
 an organic layer, disposed between the anode and the cathode, comprising a compound comprising a first ligand L A  having a structure according to Formula 1: 
 
       
         
           
           
               
               
           
         
         wherein rings A and B are each a 5 or 6-membered carbocyclic or heterocyclic ring; 
         wherein R A  and R B  each independently represent a mono substitution up to the maximum possible number of substitutions, or no substitution; 
         wherein Z 1  and Z 2  are each independently selected from the group consisting of carbon or nitrogen; 
         wherein Z 1  is a neutral donor atom; 
         wherein each R A  and R B  is independently a hydrogen or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; 
         wherein any adjacent substituents are optionally joined or fused into a ring; 
         wherein at least one pair of R B  are joined or fused into an aromatic ring; 
         wherein at least one R A  comprises (1) a spiro polycyclic alkyl fused to an aromatic ring, wherein the aromatic ring is directly bonded to ring A; or (2) a spiro polycyclic alkyl fused to ring A; 
         wherein the ligand L A  is coordinated to a metal M; 
         wherein the metal M can be coordinated to other ligands; and 
         wherein the ligand L A  is optionally linked with other ligands to comprise a tridentate, tetradentate, pentadentate or hexadentate ligand. 
       
     
     
       19. The consumer product in  claim 18 , wherein the consumer product is selected from the group consisting of flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screen, and a sign. 
     
     
       20. A formulation comprising the compound of  claim 1 .